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Revised Mulliken Electronegativities

II. Applications and Limitations


Steven G. Bratschl
University of Texas. Austin, TX 78712

In Part I of this series (I), the Mulliken electronegativity The equalized Mulliken electronegativity a., in a molecule
scale (2, 3) has been revised and extended to consider 50 or polyatomic ion may he calculated by (14,15)
elements. I t is shown that an alternate method of assign-
ment of "typical" singly bonded valence states to main
groups V-VII of the periodic table allows conversion of Mul-
liken electronegativities to the well-known Pauling units (4, where u represents the number of atoms of a particular
5) with unprecedented accuracy and solves a half-century- element in the species formula (e.g., for BFa-, U B = 1and UF
old puzzle concerning the physical dimensions of the two = 4) and q represents the net charge on the species (e.g., for
scales. BFI-, q = -1). The partial ionic charge on an atom A in the
In this work, some of the more important applications of species may he calculated by rewriting eq 2 as
Mulliken electronegativities to topics in chemical education
are discussed, problems within the Mulliken system are
identified (with suggestions for their solution where possi-
ble), and recommendations are made for future research.
Calculation of Partial ionic Charges on Combined Atoms
from Mulllken Eleclronegativities
Calculated partial ionic charges on combined atoms are Using BF4- as an example, assigning the valence states B
valuable aids in understanding and teaching periodic varia- (V = 3) = te and F (V = 1) = 14.3%s (I).
tions in chemical and physical properties (6-8).A method of
partial ionic charge calculation applicable to Mulliken elec-
tronegativities has developed from the Iczkowski-Margrave
atomic charge-energy function (9),as extended by Hinze,
Whitehead, and Jaffe (10). For multiple ionizations, the
relative energy E of an atom A is approximately a quadratic
function of the charge, 6 ~If. the energy of the neutral atom A
in a specified valence state is set a t zero, the energy of A+ is The partial ionic charges have been given to three decimal
places in this example merely to minimize round-off error.
the valence-state ionization potential, IPv,and the energy of
As discussed in the section concerning bond energy calcula-
A-is thenegative of thevalence-state electron affinity, EAv.
This gives tion, they are not accurate to this level.
Correlation ol Mulllken a and b Parameters and the
Principle of Hard and Sofl Aclds and Bases
A highly electronegative atom will usually have both a
Assuming the energy as defined by eq 1to be a continuous high valence-state ionization potential and a high valence-
and differentiable function of charge, state electron affinity. Thus, it is not surprising that "the
values of a and b for an element parallel each other" (11,12),
or that the ratio bla remains fairly constant for many ele-
ments (16). A correlation of the "typical" singly bonded
Iczkowski and Margrave (9) and Hinze, Whitehead, and valence states discussed in Part I of this series (1)gives
Jaffe (10) have equated d E ~ l d with
6 ~ electronegativity, con-
sidering the Mulliken definition (2,3) to he a special case of
eq 2, with 6~ = 0. Huheey (Sb, 11, 12) has suggested the Nalewajski (16) has reported bla = 1.52 f 0.22, from ground-
following notation: state ionization potentials and electron affinities for several
IP, + EA, elements.
a, = inherent electronegativity = XA(M)= (3) Substitution of eq 7 into eqs 5 and 6 gives
2

~XA(M)
b~= charge coefficient = -= IP,, - EA,
d6A
The calculation of partial ionic charges from the Mulliken
..
a and b Darameters is accomnlished throueh the ao~lication~~ ~

of ~anderson'sprinciple o i electronegat';vity equalization In eq. 8, N = Z ( U )= the number of atoms in the species


(fia, 7 o . I J j :"When twoor more atoms unite. their elecrrone- formula. Nalewajski (16) has derived eq 8 for neutral species
gativities become adjusted to the same inte&ediate value." (q = O), calling it the "Harmonic Mean Law." Equations
totally analogous to eqs 8 and 9, but using Pauling electrone-
gativities (4, 5) and setting bla = 1, have been suggested
recently by the author (15).
'Present address: University of Connecticut-Greater Hartford Pearson's principle of hard and soft acids and bases (17-
Campus. 85 Lawler Road. W. Hartford. CT 061 17. 20) has served as a qualitative guide for the prediction and

Volume 65 Number 3 March 1988 223


rationalization of many chemical reactions: "Hard acids pre-
fer hard bases and soft acids prefer soft bases." Classifica-
tion of chemical species as hard or soft has been made on the
basis of such properties as charge, size, electron configura-
tion, and closeness in spacing of energy levels. Over the
years, much confusion has developed over the definitions
and underlying causes of hard-soft acid-base phenomena
(8c, 20,21). In particular, hardness has often been confused
with inherent acid or base strength (21).
Evans and Huheey (22-24) have observed that typical
hard chemical species tend to have large Mulliken b parame-
ters (eq 4). More recently, Parr and Pearson (25) have sug-
gested that hardness be formally defined in this way, inter-
preting the Mulliken b parameter as the resistance of the
electronegativity of a chemical species to change in the num-
ber
~~- of electrons. Parr and Pearson have tabulated hardness
~ ~ ~~~ ~ ~

parameters for several atoms, molecules, and ions of chemi-


cal interest: for the sake of internal consistencv and because
of the frequent lack of valence-state promotion energies,
thev have used eround-state ionization ~otentialsand elec-
tn,; affinities t6roughout their work. ~bmparisonbetween
s ~ e r i e with
s - should urohahly he made with
different charges
caution.
The Mulliken b parameter for an atom A in a specified
valence state is rigorously the energy change for the process

2A(vs) - At(vs) + A-(vs) (10)


Thus, according toParr and Pearson (25),the hardness of an
Conelationof Mulliken atomic a and b parameters and atomic size.
atom A may he defined as its resistance to disproportion-
ation into A+ and A-.
Evans and Huheey (22-24) have found i t unnecessary to
consider hardness or softness explicitly in the evaluation of
the energy of homolytic bond cleavage and have suggested obvious. Thus, b, (alr)1'2 or simply a h could be used as an
that, for such processes, "hard-hard" interaction could he index of relative atomic hardness.
viewed as "small-small" interaction. In general, small atoms I t is noteworthy that the Mulliken b parameters for pure s
tend to be harder than large atoms, although exceptions are and pure pvalence states (I) often deviate widely from eqs 7,
known (8c, 17-21). Onemay therefore expect arough inverse 11, and 14. This supports the view that most pure s and p
correlation between atomic size and the Mulliken b parame- electronegativities have little direct bearing on chemistry,
ter (26). For the "typical" singly bonded valence states dis- being merely contributing terms to actual s-p hybrid elec-
cussed in Part I of this series (1). tronegativities (1).
b=
0.92 0.30 * (11) Calculation of Mulllken Group Electronegatlvltles
r
The concept of electronegativity evolved largely from the
where r is the nonpolar covalent atomic radius in nanome- desire of organic chemists to understand reaction mecha-
ters (76). nismsin terms of the inductive effects of different functional
Substitution of eq 11into eqs 5 and 6 gives groups (27). Hinze, Whitehead, and Jaffe (10) have calculat-
ed Mulliken group electronegativities a c by an iterative
method, while Huheey (11,12) has obtained both a c and bc
by plots of a., against net group charge 6c. Explicit equa-
tions for a c and bc can be derived from the work of Reed
(14):

-. Samuels. and Parr (26)


Rav. . . have derived ea 12 for neutral
species ( q = 0).
The Mulliken atomic b ~arameter,a quantitative measure
of hardness (25), is roughly relateddirectly to atomic elec-
tronegativity (eq 7) and inversely to atomic size (eq 11).
Interestingly, thedatain Part I of this series (I) indicate that In eqs 15 and 16, u represents the number of atoms of a
atoms that show positive deviations from eq 7 tend to show particular element in the group (e.g., for CH3, uc = 1and U H
negative deviations form eq 11, and vice versa. Therefore, a = 3). Using CHz as an example, assigning the valence states
combination of eqs 7 and 11should lead to a partial cancella- C(V = 4) = te and H(V = 1)= ~ ( 1 ) .
tion of errors and allow the estimation of the Mulliken b
parameter with increased accuracy. The geometric mean of
eqs 7 and 11is

as illustrated in the figure. The plotted points deviate sys-


tematically from a linear relationship, perhaps indicating Mulliken electronegativities for 35 groups are presented in
that eqs 7 and 11should not he combined with equal weights. the table. These values often differ significantly from the
Still, a general correspondence between b and (ah)'" is extensive tabulations given by Huheey (11,12), because dif-

224 Journal of Chemical Education


Mvlliken Group Electronegativitles (eV) and are probably superior because they take into account the
dependence of electronegativity on hybridization.
The Mulliken b parameters for groups are generally much
lower than the Mulliken atomic b parameters ( I ) , decreasing
CHI
C2Hr
te, s
te, s
with increasine" Nc. -
-. the number of atoms in the erouD (86.
11,12). In agreement with eq 7, the 35 groups in the table
&

CsHs 1,. S
CHO lr. 5 , h
give
COCHs tr, tr, te, s bc = (1.20 + 0.17)a,lNc (17)
COOH tr, tr. ', s
CFs
CClo
CN
18. .
te. '

di, dl
In addition to beinga measure of hardness (25), the Mulli-
ken b parameters is an inverse measure of charge capacity,
the ability to donate or withdraw charge as a function of
te. -
SiHs te. s
SiFa electronegativity change. Groups are effective reservoirs of
NNN tr, di, h charge capacity, increasingly so with increasing Nc. Charge
NH.
NO
-.
tr. v
S capacity considerations explain interesting chemical differ-
ences between atoms and arouns. such as the abilitv of
NOn
NF2
..
tr, te
groups ro funct~onboth as hette; charge donors and accep-
NCO tr, di, tr tors than atoms of wnilar inherent elecrroneaativit\
- (8h,Rd,
NCS tr, di, tr 28).
pH2 S Equations 15 and 16 do not take group structure into
OH
OCI ..,. 5 account and predict that isomeric groups have the same
electronegativity, provided that all valence states remain the
',
OClO
OCiO? ...,te, .
16.7% s, '
20% r. '
same. This is in agreement with Sanderson's principle of
electronegativity equalization (6a, 70, 13) hut has caused
0CiO3
OBrO?
OIO*
.. .20% s.
some concern (11.12). If Sanderson's orincinle is valid. and
there is theoretick sipport that it is (i9-31j, then struetur-
ON0 allv denendent inductive effects. so imnortant in organic
0NOz chemistry, should probably not be interpreted as polar ef-
OCHs fects (charge effects operating through bonds), but as field
OCsHs effects (charge-distance effects operating directly through
OCHO space) (28).
OCOCH. '. tr. h, te. s Equations 3 and 4 may be combined to give
OCN '. di, dl
SH -, S 8.21 5.71 ZPv = oA + b,12 (18)
SCN ', di, dl 10.94 3.88 3.10 2.7118

(*melinking atom 13wrinen first. EAv = a, - bA12 (19)


Eauations B a n d 19 are strictlvvalid onlvfor atoms. hut it is
.- . .- . ... of &erest to test their applicibility to gr"oups. ~nfo;tunate-
quat ti on 15. lv. eas 18 and 19 ~ r e d i cthe
t ualence-state ionization poten-
14 Equation 16.
I*Conmrted from &as described in ref 1 (ial a i d electron affinity, which are generally unavailable for
10 Ref 28. groups, so comparison with experiment is difficult. (For ex-
18 Pmbabiy lm low (see text). &pie,the isolated methyl gro"p does not maintain tetrahe-
dral HCH bond angles through the sequence CH3-, CH3.
CH3+.)Nevertheless, Reed U4) has calculated Mulliken a
and b parameters for a number of groups and stable mole-
ferent valence states have usually been assigned to singly cules via eas 15 and 16 and has then attempted to oredict
bonded atoms of elements in periodic groups V-VII (I). ionization potentials via eq 18. Reed has f&nd that eq 18
Partial ionic charge calculations with Mullikeu group elec- predicts (valence-state) ionization potentials for nonbond-
tronegativities are performed identically to those with Mul- ing electrons within f 1 0 % of the experimental (ground-
liken atomic electronegativities, that is, via eqs 5 and 6. state) values. For bondine electrons.. the .re dictions of ea 18
Using CH3F as an example, assigning the valence state F(V are 20-30% too low, whilefor antibonding electrons theyare
= 1) = 14.3% s (I). 30-70% too high. On the other hand, eq 19 predicts group
and molecular (valence-state) electron affinities that are two
to four times as large as the experimental (ground-state)
values (8e), indicating that Reed's occasionally good ioniza-
tion potential results (14) may be somewhat fortuitous. The
questionable integrity of the Mulliken b parameter in bond-
ed atoms (discussed in the following section) may lead to a
propagation of errors which is more obvious in the group
The value obtained for a,, (8.61) is the same as that obtained electron affinity because it is smaller than the group ioniza-
fromeq 5 with atomic electronegativities, and also gives 6c = tion potential.
+0.040 and 6~ = +0.112.
Mullikengroup a parameters may be converted to Pauling Calculation of Bond Energies from Mulliken
units (4, 5) as described in Part I of this series (I). The Eleclronegativities
author (28) has recently calculated group electronegativities The calculation of the stahilitv of unknown chemical sne-
directly from thermochemically derived Pauling values (5). cies is at the very heart of practical theoretical chemistry and
Both results are listed in the final two columns of the table. is a valuable teaching aid (6b, 7c). Ferreira (32) and Evans
The agreement between the two sets of values is generally and Huheey (22-24) have utilized Mulliken electronegativi-
good except for groups containing multiply bonded atoms; in ties in the calculation of "bond energies". the decrease in
such cases the converted Mulliken a parameters are higher total energy of binary molecular com~oundsrelative to iso-

Volume 65 Number 3 March 1933 225


lated atoms in their valence states. They have ascribed the tnm wrthdrswal by other. more elcrtrunegative aroma 181 groups
energy decrease to three contributing terms: !I, bd, dg, 34). In mder to accommodnrr the nohle gases. i1 has
brrn suggestrd that the word arrrnrr in Psulmg's definition be
1. The covalent energy,Ec, a lowering in energy of a molecule due to replaced by the phrase attract or hold (34).
overlap of bonding orbitals. Ec has been calculated by the aritb-
metic mean (32) or the geometric mean (22-24) of the nonpolar The following scale-independent definition of atomic or
covalent homonuclear hond energies. Evans and Huheey (22-24) group electronegativity addresses all these issues, yet re-
have also attemoted to account far oossible re~ulsionbetween mains simple enough for beginning chemistry students: elec-
lone pairs of electrons on adjacent bonded atoms. Ec becomes tronegatiuity = the ability of a n a t o m orgroup to attract or
less negative with increasing charge transfer, due to decreasing hold electrons to itself when combinine with other atoms or
overlap of handing orbitals. groups. The word combining is a dynamic term (which is not
2. The Madelung (ionic or electrostatic) energy, EM,a lowering in synonymous with combined), and is compatible with San-
energy of a molecule due to attraction of opposite charges.EMhas dersou's principle.
been calculated by a classical eoulombic model. EM becomes
more negative with increasing charge transfer and decreasing
internuelear distance. Conclusion
3. The elertnmcgativity rnerm, E x , a lowering in rnrrg). of n mole- A common misconception among chemistry teachers is
cule due 10 chargr rmnsfer irmn a les, ro a muw elertronegarivr the belief that the lack of accurate electron affinities severe-
atom 1Y.10,. E x hsr hemralculated by zim~~lrnne~~u.rapplir~1iun ly limits the application of the Mulliken electronegativity
of eq 1to all atoms in the molecule. Ex becomes more negative scale to topics in chemical education. However, Hinze and
with increasing charge transfer until electronegativity equaliza- Jaffe (35) have pointed out that this has never been a valid
tion is reached; thereafter it becomes less negative and may excuse for avoiding the Mulliken scale because the uncer-
eventually become positive. tainty in the electron affinity is always small compared to
Ferreira (32) and Evans and Huheey (22-24) have varied the electronegativity. Moreover, the accumulation of accu-
these terms with partial ionic charge to minimize the total rate, experimental electron affinities for many elements (36)
molecular energy. Their calculated hond energies agree rea- has nullified this areument.
sonably well with experiment. However, because E, and EM In the author's oGnion, future research into the Mulliken
work in opposition to the total energy and because EMis electroneeativitv
main objectives:
- -
" svstem should be directed toward two
always more negative than the Ec, it replaces (6c, 7d, 8f, 22-
24, 32), the total energy minimization procedure leads to 1. The evaluation of reliable Mulliken electronegativities for the
charge transfer that is significantly larger than predicted by transition elements.
eqs 5 and 6. 2. The development of an extensive method of bond-energy calcula-
Ferreira (32) and Evans Huheey (22-24) have speculated tion, applicable to a wide variety of compounds, and including a
that the discrepancy in partial ionic charge could indicate quantitative relationship between the Mulliken b parameter
that Sanderson's principle of electronegativity equalization (dXn(M)ldb~) and internuclear distance.
(6a, 7a, 13). although useful, is only approximately true.
Ferreira (32) has made the provocative comment that San- It is I~elievedthat two major theoretiraldiffirultiesremain
derson's principle is valid only if there are no interactions associated with the Mulliken system:
between the atoms, that is, if the "bonded" atoms are sepa- 1. The need for a generalized method of valence state assignment
rated hy an infinite distance! (1).This is a very serious problem.
However, Sanderson's principle has received support 2. The need for a better understanding of the importanceof outer d-
through the quantum-mechanical arguments of density orbital participation in chemical bonding (I).
functional theory (29, 301, and Politzer and Weinstein (31)
have shown that it can he derived without specifying any As long as the concept of atoms in molecules remains
particular theoretical model. Therefore, i t appears that Fer- useful. it is likelv that the electroneeativitv conceDt will be
reira's (32) comment about Sanderson's principle should retainkd in someuform.The Mulliken-system offers-a simple,
nrobahlv he directed instead toward the Iczkowski-Mar- elegant definition of absolute electroneeativitv that has
grave atomic charge-energy function (91, eq 1.It is suggested withstood meticulous theoretical scrutiny-lf the-theoretical
that the Mulliken b narameter ( s u ~ ~ o s e d al vmeasure of difficulties stated above can be resolved, it is predicted that
dXA(M)/d6~) decreasks from its isoi&ed-atom value of IPv the Mulliken system of electronegativity is the one that will
- EAv (eq 4) as an atom approaches other atoms, due to the endure after all the others have been deposited into the
interaction of electrical fields. The possibility of a distance- archives of chemical history.
dependent Mulliken b parameter preserves Sanderson's
principle but also accounts for the results of Ferreira (32) Literature Cited
and Evans and Huheey (22-241, because charge transfer 1. Brabeh, S. G. J . ChmL Educ., in press.
2. Mu1iiken.R. S. J. ChanPhya. 1934,2,782.
increases as b decreases (eq 6). 3. Mulliken,R. S. J. ChemPhys. 1935.3.573.
4. Pau1ing.L. J.Am. Chem.Sac. 1932, S4.3570.
5. A1lred.A. L. J . Inorg. NucLChrrn. 1961.17.215.
A Scale-Independent Definition of Atomic or Group 6. Sanderaan,R. T. Inorganic Chemistry: Reinhold: New York,1967:la) pS1,lbl pp 121-
138, 14 pp 124-130, Id) p 305.
Electronegativity 7. Sanderaan, R. T. Polor Coudenee: Aesdemie: New York, 1983:la) pp 37-39, lb) p 41,
Pauling's original definition of electronegativity, "The
nower of an atom in a molecule to attract electrons to itself'
S~ ~

(33), needs to be revised to accommodate our modern views 9. Ierkowski, R. P.:Margrave, J. L. J . Am. Chom. Soc. 1961,83,3647.
of the electronegativity concept: 10. Hinze,J.; Whitehead,M. A.:snd Jsffe,H. H.J . A m , Chsm.Soc. 1963.85,148.
n. Huheey, J. E. J. Phys Chem 1965.69.3284,
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time. A better word is ability. 13. Sanderson, R. T. Science 1951.114.670.
14. Reed.J. L. J.Phvr. Cham. 1981.85.148.
2. The word atom should be replaced by the phrase atom or group. 15. ~~st&h,S.G. J . C ~ ~ ~ . E 1984,61,588.
~ U C .
16. Nalewajski. R. F. J. Phys Chem. 1985.89,2831.
3. Pauling's definition implies that different bonded atoms in a 17. Pearsun, R. G. J.Arn.Cham.Soc. 1963,85. 3533.
single chemical species have different electronegativities. Thus, 16. Pearson, R. G. J. Chzm. Edur. 1968.45.581.
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(6a, 70,13). 20. Pearson, R. G. Hard and Soft Acids ond Boaer: Dowden, Hutchinson and Ross:
Stroudshurg, PA, 1973.
4. Pauling's definition excludes the noble gases, whose very high , . B. he ~ e w i a~ c i d - ~ o sConcepts:
21. ~ e n r e nW e A" Oueruialu: Wiiey: New York. 1980:
electronegativitiesindicate only their relative resistance to elec- pp 253-303.

226 Journal of Chemical Education


22. Eusna, R. 8.; H u h w , J. E. J. lnorg. Nurl. Cham. 1970,32.373. 30. Donnelly, R . A . ; P r r R . G. J. Chem Phyr. 1918,69,4431.
23. Huheey, J.E.:Evans, R. S. J I n o r g . NurLChrm. 1970.32.383. 31. Politrer, P.; Weinsbin, H. J.Chern.Phy% 1979. 71,4218.
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25. Parr, k.G . ; ~ e a m R.G.
~ ~ ; J.~rn.?hem.Suc, 1983, i05.7512. 33. Pauling, L. TheNorvre oflhs Chm&d Band: CornellUniversity: Ithscs, NY, 1939:p
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cs
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Volume 65 Number 3 March 1988 227

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